US6831030B2 - High transmittance glass sheet and method of manufacturing the same - Google Patents

High transmittance glass sheet and method of manufacturing the same Download PDF

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US6831030B2
US6831030B2 US10/236,397 US23639702A US6831030B2 US 6831030 B2 US6831030 B2 US 6831030B2 US 23639702 A US23639702 A US 23639702A US 6831030 B2 US6831030 B2 US 6831030B2
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glass sheet
glass
high transmittance
transmittance
sheet according
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US20030125188A1 (en
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Akihiro Koyama
Isamu Kuroda
Nobuyuki Yamamoto
Yasunori Seto
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Nippon Sheet Glass Co Ltd
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Nippon Sheet Glass Co Ltd
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Priority to US10/772,715 priority Critical patent/US7071134B2/en
Priority to US10/772,835 priority patent/US6903037B2/en
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    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/078—Glass compositions containing silica with 40% to 90% silica, by weight containing an oxide of a divalent metal, e.g. an oxide of zinc
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/083—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C4/00—Compositions for glass with special properties
    • C03C4/0085—Compositions for glass with special properties for UV-transmitting glass
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C4/00—Compositions for glass with special properties
    • C03C4/10—Compositions for glass with special properties for infrared transmitting glass

Definitions

  • the present invention relates to a high transmittance glass sheet of soda-lime-silica glass manufactured mainly by a float process. More specifically, this invention relates to a high transmittance glass sheet that allows the formation of nickel sulfide (NiS) in a process of melting a glass raw material to be suppressed effectively.
  • NiS nickel sulfide
  • NiS nickel sulfide
  • soda-lime-silica glass sheets are tempered to be used for buildings, vehicles, cover glass plates for solar cell panels, solar water heaters or the like.
  • a glass sheet is heated to a temperature near the softening point (about 600° C.) of the glass sheet. Then, the glass sheet is quenched so that compressive stress layers are generated in surfaces of the glass sheet.
  • NiS When NiS is contained in a tempered glass sheet, NiS is present in an ⁇ phase that is stable at about 350° C. or higher, and undergoes phase transition with the lapse of time to a ⁇ phase that is more stable at room temperature. This phase transition causes NiS particles to expand in volume. As a result of this, micro cracks may appear in the vicinity of the NiS particles.
  • a tensile stress layer exists, having a thickness of about two-thirds that of the glass sheet. When cracks appear in the tensile stress layer, the cracks run rapidly to cause spontaneous fracture of the tempered glass sheet.
  • soaking has been known.
  • tempered glass sheets are heated to 300° C. or lower in a furnace (soaking furnace). Then, the tempered glass sheets are maintained in the furnace for a predetermined time, so that NiS undergoes phase transition from an ⁇ phase to a ⁇ phase. This forces the tempered glass into breakage. In this manner, defective glass products containing NiS are eliminated.
  • JP 9(1997)-169537 A discloses a method of manufacturing a soda-lime-silica glass in which 0.01 to 0.15 wt. % of a zinc compound such as zinc nitrate and zinc sulfate is added to raw materials, thereby allowing the formation of NiS to be suppressed.
  • a zinc compound such as zinc nitrate and zinc sulfate
  • a high transmittance glass sheet more specifically, a glass sheet having a light color and a high transmittance be used for an interior glass, a showcase, a display case, a high transmittance non-colored window glass, a high transmittance non-colored mirror, a glass substrate for a solar cell panel, a cover glass plate for a solar cell panel, a solar water heater, a material for a high solar-heat transmittance window glass, and a flat display substrate glass such as a front panel or the like.
  • no high transmittance glass sheet has been known so far that is suitable for industrial mass production.
  • a high transmittance glass sheet according to the present invention is formed of a soda-lime-silica glass composition containing, expressed in wt. %, less than 0.020% of total iron oxide and 0.006 to 2.0% of zinc oxide.
  • total iron oxide denotes an amount of iron oxide in terms of Fe 2 O 3 . All of the iron in the composition is counted as Fe 2 O 3 , even if it exists as FeO.
  • the soda-lime-silica glass composition constituting the high transmittance glass sheet according to the present invention contains less than 0.020 wt. % (less than 200 ppm) of total iron oxide.
  • total iron oxide is contained in an amount of not less than 0.005 wt. % as will be described later.
  • zinc oxide should be contained, in terms of ZnO, in an amount of not less than 0.006 wt. % (not less than 60 ppm).
  • the addition of zinc oxide does not cause an increase in light absorption in the visible light region. It has been found to be desirable for the suppression of NiS formation that the content of zinc oxide be increased in inverse proportion to the content of total iron oxide. When the content of total iron oxide has a value near 200 ppm, it is required that ZnO be contained in an amount of not less than 60 ppm.
  • ZnO is contained in an amount of not less than 180 ppm. More preferably, when the content of total iron oxide has a value near 200 ppm, ZnO is contained in an amount of not less than 100 ppm, and when the content of total iron oxide is 50 ppm, ZnO is contained in an amount of not less than 300 ppm.
  • ZnO In manufacturing a high transmittance glass, in order to prevent ZnO from volatilizing during melting to damage a furnace, ZnO should be contained in an amount of not more than 2.0 wt. % (not more than 20,000 ppm). In the case where a float bath is used for forming a glass sheet, in order to prevent ZnO that has volatilized and condensed in the float bath from dropping onto a glass ribbon to form a defect, ZnO is used desirably in an amount of not more than 5,000 ppm, and more desirably in an amount of not more than 1,000 ppm.
  • This problem which is caused by dropping of a condensed material that has volatilized, does not occur in the case where a glass sheet is manufactured, instead of using the float bath, for example, by a roll out process in which molten glass is rolled using a roller with an uneven (a predetermined pattern) or an even surface, and by a process in which molten glass that has been allowed to pass through a slit or overflow from a melting tub is drawn.
  • the glass composition has contents of the total iron oxide and the zinc oxide whose values fall preferably within a range defined by a square ABCD formed by connecting Point A (200, 60), Point B (200, 20,000), Point C (50, 20,000), and Point D (50, 180) in this order, more preferably within a range defined by a square A′BCD′ formed by connecting Point A′ (200, 100), Point B (200, 20,000), Point C (50, 20,000), and Point D′ (50, 300) in this order, and most preferably within a range defined by a square A′B′C′D′ formed by connecting Point A′ (200, 100), Point B′ (200, 5,000), Point C′ (50, 5,000), and Point D′ (50, 300) in this order.
  • a square ABCD formed by connecting Point A (200, 60), Point B (200, 20,000), Point C (50, 20,000), and Point D (50, 180) in this order
  • a square A′BCD′ formed by connecting Point A′ (200, 100),
  • the present invention also provides a method of suppressing formation of nickel sulfide in a high transmittance glass sheet having a solar radiation transmittance of 87.5% or higher and/or a visible light transmittance of 90.0% or higher on a basis of a 4.0 mm thick glass sheet.
  • a glass raw material is prepared so that a content of total iron oxide in terms of Fe 2 O 3 is less than 0.020 wt % and a content of zinc oxide is 0.006 to 2.0 wt. %, and the glass raw material is melted.
  • the content of zinc oxide required to suppress the formation of nickel sulfide particles in a glass composition increases as the content of total iron oxide is decreased when the content of the total iron oxide in the glass is in the range of 0.006 to 0.060 wt. %. Since zinc oxide materials are costly compared with other raw materials, it would be cost effective to use zinc oxide in the least possible amount required to suppress the formation of nickel sulfide particles. Therefore, in manufacturing soda-lime glasses successively, when the content of total iron oxide in a glass composition is decreased over time, preferably, the content of zinc in the glass composition is increased accordingly within the range of 0.006 to 0.50 wt. % (60 to 5,000 ppm). Conversely, when the content of the total iron oxide in the glass composition is increased over time, preferably, the content of zinc in the glass composition is decreased accordingly in the above range.
  • Examples of zinc compounds for zinc oxide (ZnO) that should be added to a raw material include an inorganic zinc compound such as zinc nitrate (Zn(NO 3 ) 2 .6H 2 O), zinc sulfate (ZnSO 4 .7H 2 O), a zinc halide (e.g.
  • zinc fluoride ZnF 2 .4H 2 O
  • zinc bromide ZnBr 2
  • zinc chloride ZnCl 2
  • zinc iodide ZnI 2
  • zinc phosphate Zn 3 (PO 4 ) 2 .4H 2 O
  • organic zinc compound such as zinc benzoate (Zn(C 6 H 5 CO 2 ) 2 ) and zinc acetate (Zn(CH 3 CO 2 ) 2 .2H 2 O).
  • FIG. 1 is a graph showing a preferred relationship between the content of total iron oxide and the content of zinc oxide in a glass composition according to the present invention.
  • FIG. 2 is a graph showing a relationship between the respective contents of T-Fe 2 O 3 and CeO 2 and a fluorescence intensity ratio.
  • FIG. 3 is a graph showing a relationship between the content of Fe 2 O 3 and a number of NiS particles formed in a soda-lime-silica glass.
  • FIG. 4 is a graph showing a relationship between an amount of Ni added and the content of ZnO required to reduce the number of NiS particles to half in a soda-lime-silica glass.
  • the high transmittance glass sheet according to the present invention is formed of a glass composition containing total iron oxide and zinc oxide as described above. In the following description, the glass composition will be explained in greater detail.
  • the high transmittance glass sheet according to the present invention has the following features. That is, the glass sheet is formed of a soda-lime-silica glass composition that contains in addition to the zinc oxide, expressed in wt. %, 0.005 to less than 0.020% of total iron oxide (hereinafter, referred to as T-Fe 2 O 3 ) in terms of Fe 2 O 3 , less than 0.008% of FeO, and 0 to 0.25% of cerium oxide, and has a ratio (hereinafter, referred to as a FeO ratio) of the content of FeO in terms of Fe 2 O 3 to the content of T-Fe 2 O 3 of lower than 40%.
  • T-Fe 2 O 3 total iron oxide
  • FeO ratio a ratio of the content of FeO in terms of Fe 2 O 3 to the content of T-Fe 2 O 3 of lower than 40%.
  • the high transmittance glass sheet When measurements are made on a 4.0 mm thickness basis, the high transmittance glass sheet preferably has a solar radiation transmittance of 87.5% or higher, a visible light transmittance as determined using the CIE standard illuminant C of 90.0% or higher, a dominant wavelength as determined using the illuminant C of 540 to 580 nm, and an excitation purity as determined using the illuminant C of 0.35% or lower.
  • the content (wt. %) of the zinc oxide is expressed by a value of an amount of the zinc oxide added with respect to a total amount of 100 wt. % of the other components.
  • the high transmittance glass sheet has the following features. That is, the glass sheet is formed of a composition that is substantially free from cerium oxide (the content of CeO 2 is less than 0.005 wt. %) and has a FeO ratio of equal to or higher than 22% to lower than 40%. In this case, when a measurement is made on a 4.0 mm thickness basis, the high transmittance glass sheet has an excitation purity as determined using the illuminant C of 0.25% or lower. This composition allows a high transmittance and extremely light colored glass sheet.
  • a high transmittance glass sheet that is formed of a glass composition containing 0 to 0.005 wt. % of cerium oxide, not more than 0.03 wt. % of manganese oxide, and not more than 0.01 wt. % of vanadium oxide can achieve the following.
  • the transmittance (in the near-infrared region) at a wavelength of 1,000 nm can be improved by not less than 0.1%, and in some cases, by not less than 0.3% with respect to that of the glass sheet before being exposed to the ultraviolet radiation.
  • the solar radiation transmittance and the visible light transmittance of the high transmittance glass sheet also can be increased to 90.0% or higher and 90.5% or higher, respectively.
  • the high transmittance glass sheet has the following features. That is, the high transmittance glass sheet is formed of a composition that contains, expressed in wt. %, 0.02 to 0.25% of cerium oxide, and has a FeO ratio of lower than 22%. When measurements are made on a 4.0 mm thickness basis, the high transmittance glass sheet has a solar radiation transmittance of 90.0% or higher and a visible light transmittance as determined using the illuminant C of 90.5% or higher. This allows a high transmittance glass sheet to be obtained that exhibits a high transmittance particularly in a region ranging from the visible region to the near-infrared region.
  • a high transmittance glass sheet is preferred that contains, expressed in wt. %, 0.025 to 0.20% of cerium oxide, and has a ratio of a fluorescence intensity at a wavelength of 395 nm to a fluorescence intensity at a wavelength of 600 nm (f(395 nm)/f(600 nm), hereinafter, referred to also as a fluorescence intensity ratio) of 10 or higher when subjected to ultraviolet irradiation at a wavelength of 335 nm.
  • a high transmittance glass sheet is desired that contains 0.03 to 0.15 wt. % of cerium oxide and has a fluorescence intensity ratio of 15 or higher.
  • a high transmittance glass sheet is desired most that contains 0.05 to 0.12 wt. % of cerium oxide and has a fluorescence intensity ratio of 25 or higher, since the glass sheet allows most efficient conversion of ultraviolet light into visible light.
  • the above-mentioned soda-lime-silica glass composition according to the present invention contains, in addition to the iron oxide, the zinc oxide and the cerium oxide that are described above, as components constituting a base glass composition, expressed in wt. %, 65 to 80% of SiO 2 , 0 to 5% of Al 2 O 3 , 0 to 7% of MgO, 5 to 15% of CaO, where a total content of MgO and CaO is more than 7% and not more than 17%, 10 to 18% of Na 2 O, 0 to 5% of K 2 O, where a total content of Na 2 O and K 2 O is 10 to 20%, and 0.05 to 0.3% of SO 3 .
  • the content of the above-mentioned zinc oxide is expressed by an amount of the zinc oxide added with respect to a total amount of 100% of the above components constituting the base glass composition.
  • the total content of MgO and CaO is 10 to 17 wt. %, and the content of SO 3 is 0.08 to 0.15 wt. %.
  • the content of MgO be 0.5 to 7 wt. % since this allows meltability and formability to be improved.
  • the content of Al 2 O 3 be 0.5 to 5 wt. % since this allows water resistance to be improved.
  • composition of the high transmittance glass sheet according to the present invention will be described in terms of the components other than the zinc oxide described earlier.
  • respective contents of the components are expressed in wt. %.
  • iron oxide is present in forms of Fe 2 O 3 and FeO.
  • Fe 2 O 3 serves to enhance an ultraviolet-absorbing ability
  • FeO serves to enhance a heat-absorbing ability.
  • the content of T-Fe 2 O 3 (a total content of Fe 2 O 3 and FeO in terms of Fe 2 O 3 ) is less than 0.020%, and preferably, the content of FeO is less than 0.008%, and the FeO ratio is lower than 40%.
  • T-Fe 2 O 3 When the content of T-Fe 2 O 3 is less than 0.005%, it is necessary to use high purity materials having low iron contents. This leads to a substantial cost increase. Thus, preferably, T-Fe 2 O 3 is contained in an amount of not less than 0.005%.
  • a glass sheet When used for a glass substrate and a cover glass plate for a solar cell panel using amorphous silicon, a glass sheet preferably has a high transmittance with respect to light having a wavelength in the vicinity of 500 to 600 nm and exhibits moderate solar radiation absorption.
  • the content of T-Fe 2 O 3 is in the above-mentioned range, the content of FeO is more than 0.003% and less than 0.008%, and the FeO ratio is equal to or higher than 22% and lower than 40%.
  • a glass sheet When used for a glass substrate and a cover glass plate for a solar cell panel using crystalline silicon, preferably, a glass sheet has a high transmittance with respect to light having a wavelength in the vicinity of 1,000 nm.
  • the content of T-Fe 2 O 3 is in the above-mentioned range, the content of FeO is less than 0.004%, and the FeO ratio is lower than 22%.
  • Cerium oxide (CeO 2 ) is effective in regulating the content of FeO and the FeO ratio. Particularly, in order to attain a low FeO content and a low FeO ratio required when a high transmittance at a wavelength in the vicinity of 1,000 nm is desired, preferably, CeO 2 is added in an amount of 0.02 to 0.25%.
  • FIG. 2 a relationship between the content of CeO 2 and a fluorescence property is shown in FIG. 2 . As shown in FIG. 2, it was found that ultraviolet light was absorbed and converted to visible light most effectively when the content of CeO 2 was in a given range.
  • a high transmittance glass sheet could be obtained that contained less than 0.06% of T-Fe 2 O 3 and 0.025 to 0.20% of CeO 2 , thereby achieving a fluorescence intensity ratio of 10 or higher, a fluorescence intensity ratio of 15 or higher when the content of CeO 2 was 0.03 to 0.15%, and a fluorescence intensity ratio of 25 or higher when the content of CeO 2 was 0.05 to 0.12%.
  • the high transmittance glass sheet described above is suitable for use for an interior material, a glass for a showcase or the like particularly because the glass sheet takes on a fluorescent color with gradations when ultraviolet light is incident on an edge surface of the glass sheet from a cross sectional direction.
  • the above-mentioned high transmittance glass sheet is used most suitably since the glass sheet allows energy in the ultraviolet region that hardly contributes to power generation to be converted into light in the visible region, thereby allowing the power generation efficiency to be enhanced.
  • SiO 2 is a main component forming a skeleton of the glass.
  • the content of SiO 2 is less than 65%, the durability of the glass is decreased, and when the content of SiO 2 is more than 80%, melting of the glass is hindered.
  • Al 2 O 3 serves to improve the durability and the water resistance of the glass.
  • the content of Al 2 O 3 should be 0 to 5%.
  • the content of Al 2 O 3 is not less than 0.5%.
  • the content of Al 2 O 3 is not more than 2.5%. More preferably, the content of Al 2 O 3 is in the range of 1.0 to 2.5%.
  • MgO and CaO serve to improve the durability of the glass and regulate the liquidus temperature and the viscosity of the glass in a forming process.
  • MgO allows a low liquidus temperature to be maintained when contained in a moderate amount.
  • the content of MgO is preferably more than 0.5%, and more preferably not less than 2%.
  • the content of MgO exceeds 7%, the liquidus temperature is increased excessively.
  • the content of CaO is less than 5%, the meltability is degraded.
  • the content of CaO exceeds 15%, the liquidus temperature is increased.
  • the content of CaO is not more than 13%.
  • the total content of MgO and CaO is not more than 7%, the durability of the glass is decreased. Conversely, when the total content exceeds 17%, the liquidus temperature is increased. Thus, more preferably, the total content is not more than 15%.
  • the total content of MgO and CaO is as small as, for example, less than 10%, it is required that the content of Na 2 O be increased so that the degradation of the meltability and an increase in viscosity of a melt are compensated. This leads to a cost increase and a decrease in chemical durability of the glass.
  • the total content of MgO and CaO is not less than 10%.
  • Both Na 2 O and K 2 O serve to accelerate melting of the glass.
  • the content of Na 2 O is less than 10% or when a total content of Na 2 O and K 2 O is less than 10%, only a poor effect of accelerating glass melting can be obtained. It is not preferable that the content of Na 2 O exceeds 18% or the total content of Na 2 O and K 2 O exceeds 20% since this results in a decrease in the durability of the glass.
  • the content of Na 2 O is preferably not more than 15%, and more desirably not more than 14.5%. Since a material cost of K 2 O is high compared with Na 2 O, K 2 O is not an indispensable component. Even when K 2 O is used, it is not preferable that the content of K 2 O exceeds 5%.
  • SO 3 serves to accelerate clarification of the glass.
  • the content of SO 3 is less than 0.05%, a sufficient clarifying effect cannot be attained by a regular melting method.
  • the content of SO 3 is more than 0.1%.
  • SO 2 produced as a result of decomposition of SO 3 remains in the glass in the form of a bubble, and SO 3 dissolved in the glass becomes more likely to produce bubbles by reboiling.
  • TiO 2 can be added in a proper amount for the purposes of enhancing an ultraviolet-absorbing ability or the like as long as the amount is in the range that allows the optical properties that are the intended properties of the present invention not to be impaired.
  • the content of TiO 2 is limited to a low level in the range of less than 0.2%.
  • the effect of the present invention is not impaired.
  • these components create adverse impacts such as a cost increase, shortening a furnace life, release of harmful substances into the air or the like.
  • the glass composition should be substantially free from these components.
  • cerium oxide in an amount in the range defined in the above description is used, in view of the effect of cerium oxide and an ultraviolet-absorbing effect as another particular effect of cerium oxide.
  • an oxidizing agent other than cerium oxide for example, manganese oxide may be added in an amount in the range of not more than 1% in combination with cerium oxide or as an only oxidizing agent.
  • SnO 2 may be added as a reducing agent in an amount in the range of not more than 1%.
  • at least one selected from the group consisting of Se, CoO, Cr 2 O 3 , NiO, V 2 O 5 , MoO 3 or the like may be added as a coloring agent, in an amount in the range that allows the high transmittance that is the intended property of the present invention not to be impaired.
  • the coloring agent is added in an excessive amount, a color tone is intensified and the visible light transmittance is lowered.
  • these compounds are not added practically.
  • the content of V 2 O 5 is not more than 0.01 wt. %.
  • the effect of the high transmittance glass according to the present invention can be attained effectively when the high transmittance glass is subjected to quenching (tempering).
  • the high transmittance glass sheet according to the present invention is highly demanded particularly in use for a solar cell panel.
  • an anti-reflecting film and a conductive film can be formed on the glass sheet. Even when these films are formed on the glass sheet, the glass properties are not affected. Further, regardless of whether these films are formed, the glass sheet can be subjected to processing involving heating such as tempering and bending. Generally, in rapidly cooling for tempering, the high transmittance glass sheet is heated to a temperature near the softening point of the glass sheet, and then cooled rapidly by being brought into contact with cold air or other fluids.
  • the high transmittance glass sheet according to the present invention generally has a thickness of 0.3 mm to 30 mm and is suitable for use for an interior glass, a showcase, a display case, a high transmittance non-colored window glass, a high transmittance non-colored mirror, a glass substrate for a solar cell panel, a cover glass plate for a solar cell panel, a solar water heater, a high solar-heat transmittance window glass, a window glass for a microwave oven, or a flat display substrate glass such as a front panel or the like.
  • Composition No. 1 represents soda-lime-silica glass having a Fe 2 O 3 content of less than 0.02 wt. %
  • Composition No. 2 represents soda-lime-silica glass having a Fe 2 O 3 content of 0.05 wt. %.
  • Glass batch materials of Samples 4 to 47 were prepared in the following manner. That is, with respect to each of these two types of raw materials, a powder of Ni metal having a particle diameter of 149 ⁇ m and a powder of zinc nitrate (Zn(NO 3 ) 2 .6H 2 O) or zinc sulfate (ZnSO 4 .7H 2 O) are added in the respective amounts shown in Tables 3 and 4.
  • a and B in the column titled “additive” represent zinc sulfate (ZnSO 4 .7H 2 O) and zinc nitrate (Zn(NO 3 ) 2 .6H 2 O), respectively.
  • a batch of these materials was put in an alumina crucible having a capacity of 250 cc and preheated at a temperature of 600° C. for 30 minutes. Then, the batch was inserted in an electric furnace maintained at a temperature of 1,370° C., and the temperature of the electric furnace was raised to 1,400° C. in 10 minutes. After being maintained at this temperature for 2.2 hours, the batch was taken out of the electric furnace and cast out to be annealed to room temperature, so that a glass sheet was obtained.
  • Glass batch materials having compositions shown in Tables 5 to 7, in which the respective contents are expressed in terms of oxide and in wt. %, were prepared using low-iron silica sand, alumina, limestone, dolomite, soda ash, salt cake, magnesium oxide, cerium oxide, manganese dioxide, zinc sulfate (ZnSO 4 .7H 2 O), and a carbon-based reducing agent. Each batch of these materials was heated in an electric furnace to a temperature of 1,450° C. to be melted. After four hours of melting, the batch was poured onto a stainless steel plate and annealed to room temperature, so that a glass sheet having a thickness of about 10 mm was obtained. In the tables, the values of concentration are expressed in wt. %.
  • the surface of the glass sheet was ground so that a glass sheet sample having a thickness of 4.0 mm was obtained.
  • measurements were performed using the illuminant C for optical properties that are a visible light transmittance, a dominant wavelength, an excitation purity, a solar radiation transmittance, and a fluorescence intensity ratio.
  • the fluorescence intensity ratio was determined in the following manner. That is, each of the samples described above was subjected to ultraviolet irradiation at a wavelength of 335 nm, and a fluorescence intensity was determined at the respective wavelengths.
  • fluorescence intensity ratio (fluorescence intensity at 395 nm/fluorescence intensity at 600 nm) as an index of the fluorescence intensity.
  • water resistance was evaluated by determining an elution amount of Na 2 O (mg) according to JIS 3502. The respective values of the optical properties and the water resistance of each sample as the results of the measurements are shown in Tables 5 to 7.
  • Example 7 9 10 11 12 SiO 2 71.7 71.7 71.6 71.6 71.5 71.5 Al 2 O 3 1.7 1.7 1.7 1.7 1.7 MgO 4.2 4.2 4.2 4.2 4.2 4.2 4.2 CaO 8.5 8.5 8.5 8.5 8.5 Na 2 O 13.0 13.0 13.0 13.0 13.0 K 2 O 0.7 0.7 0.7 0.7 0.7 SO 3 0.12 0.12 0.12 0.12 0.12 0.12 T—Fe 2 O 3 0.015 0.015 0.015 0.015 0.015 0.015 0.015 0.015 0.015 TiO 2 0.02 0.02 0.02 0.02 0.02 0.02 CeO 2 0 0.04 0.06 0.10 0.14 0.20 MnO 2 0 0 0 0 0 0 0 Total 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 10
  • 0.006 to 0.20 wt. % of zinc oxide is contained in a soda-lime-silica glass containing total iron oxide in terms of Fe 2 O 3 in an amount of less than 0.02 wt. %, and thus a sufficient effect of reducing or eliminating the formation of NiS particles can be attained, thereby allowing an improved quality glass product to be obtained.
  • the addition of the zinc oxide has almost no influence on visible light transmittance and ultraviolet transmittance, and also has no influence on physical property values of the glass in terms of a coloring property, viscosity, expansion or the like.
  • the general glass quality can be maintained, while securing high transmittance, thereby achieving a substantial advantage from a practical viewpoint.
  • the present invention allows manufacturing of glass products containing almost no NiS.
  • a heating (soaking) process for removing glasses containing NiS can be omitted after a quench tempering process, thereby allowing a manufacturing cost to be reduced.
  • a rate of glass breakage caused in soaking can be lowered, thereby allowing product yield to be improved.

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US20100179048A1 (en) * 2007-09-21 2010-07-15 Saint-Gobain Glass France Silico-sodo-calcic glass sheet
US8318621B2 (en) * 2007-09-21 2012-11-27 Saint-Gobain Glass France Silico-sodo-calcic glass sheet
US20100126218A1 (en) * 2008-11-21 2010-05-27 Ppg Industries Ohio, Inc. Method of reducing redox ratio of molten glass and the glass made thereby
US8304358B2 (en) * 2008-11-21 2012-11-06 Ppg Industries Ohio, Inc. Method of reducing redox ratio of molten glass and the glass made thereby
US20120132269A1 (en) * 2010-05-20 2012-05-31 Cardinal Fg Company Glass substrates for high temperature applications
US8664132B2 (en) 2010-09-03 2014-03-04 Ppg Industries Ohio, Inc. High transmittance glass
US20120234368A1 (en) * 2011-03-09 2012-09-20 Saint-Gobain Glass France Substrate for photovoltaic cell
US8940996B2 (en) * 2011-03-09 2015-01-27 Saint-Gobain Glass France Substrate for photovoltaic cell
US11306021B2 (en) 2018-11-26 2022-04-19 Owens Coming Intellectual Capital, LLC High performance fiberglass composition with improved elastic modulus
US11524918B2 (en) 2018-11-26 2022-12-13 Owens Corning Intellectual Capital, Llc High performance fiberglass composition with improved specific modulus

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US6903037B2 (en) 2005-06-07
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CN1408663A (zh) 2003-04-09
US20040162212A1 (en) 2004-08-19
US7071134B2 (en) 2006-07-04
EP1291330A2 (de) 2003-03-12
EP1291330A3 (de) 2004-02-25
CN1872749A (zh) 2006-12-06
CN1872749B (zh) 2010-04-14
CN1286755C (zh) 2006-11-29
US20030125188A1 (en) 2003-07-03

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